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INORGANIC CHEMISTRY · 2024 · IF 4.3

AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2): A Series of Ionic Cocrystals as Promising UV Birefringent Materials with Large Birefringence and Wide Band Gap

Mengmeng Zhu,Junbo Wang,Lei Hou,Yiwen Yuan,Lili Liu,Yaoqing Chu,Chunmei Huang

The design and syntheses of new birefringent crystals will be of great importance in commercial applications and materials science. A series of ultraviolet (UV) birefringent crystals, AX·(H2SeO3)n (A = K, Cs; X = Cl, Br; n = 1, 2), with large sizes up to 23 × 6 × 3 mm3, was successfully synthesized by simple aqueous solution method. These four compounds belong to three different space groups. Isomorphic KCl·(H2SeO3)2 and CsCl·(H2SeO3)2 crystallize in the P1¯ space group, while CsBr·(H2SeO3)2 and CsCl·H2SeO3 crystallize in the P21/m and P21/c space groups, respectively. They exhibit cocrystal structures composed of [2(H2SeO3)]∞ and [AX]∞ frameworks, ingeniously inheriting the large optical anisotropy of selenite and the wide band gap of alkali metal halide. And it proves that these compounds indeed possess large birefringence (0.1–0.17 at 532 nm) and short UV cutoff edges (227–239 nm), achieving a balance of optical properties. This research affords a simple and viable strategy for the design and syntheses of new UV birefringent crystals. Besides, it is also found that the n value and ionic size (A and X ions) have important influences on the crystal structures and optical properties of AX·(H2SeO3)n. And this will promote further understanding of the alkali metal halide selenite family.

研究领域: 材料科学 · 晶体工程 · 光学材料 · 无机化学
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CHEMISTRY OF MATERIALS · 2024 · IF 7.2

Mixed Anionic M(S/X)6 Polyhedra as Symmetry-Breaking Motifs to Enhance the Infrared Nonlinear Optical Response in Y–M–S–X (M = Ga, Ge; X = Cl, Br)

Yan Guo,Bin-Wen Liu,Chao-Hong Xie,Wen-Fa Chen,Ming-Xin Li,Xiao-Ming Jiang,Guo-Cong Guo

Rare-earth infrared nonlinear optical (IR NLO) compounds have garnered significant attention due to their abundant electronic structures. However, their NLO efficiency has been relatively modest, attributed to the localization of valence electron shells in rare-earth metals. Traditional design strategies for IR NLO materials have predominantly focused on MQ4 (M = metal, Q = S or Se) tetrahedra, with limited exploration of MQ6 octahedra. We introduce a novel approach to enhance NLO effects by incorporating distorted mixed anionic octahedral M(S/X)6 groups. To illustrate this strategy, we undertake structure modification and optimization of IR NLO performance using the Y–Ga–Ge–S system as an example. The synthesis of a new rare-earth chalcogenide, Y6Ga2GeS14 (1), serves as a foundation. Further halogen atom substitution yields Y6Ga4.2S13.6Cl3.4 (2), Y6Ga2.83Ge2S16.75Cl (3), and Y6Ga2.83Ge2S16.5Br1.5 (4). All compounds demonstrate remarkable NLO performance, including moderate NLO coefficients (0.17–0.70 × AgGaS2), large laser-induced damage thresholds (LIDTs) (3.78–6.19 × AgGaS2), and a broader transmission range (0.5–14.9 μm). The incremental enhancement of NLO efficiency in compounds 1–4 can be attributed to symmetry breaking induced by halogen atom substitution and increased distortion of the octahedral M(S/X)6 motifs in their structures, validating the effectiveness of our strategy. Notably, this strategy concurrently increases the band gap and LIDT, overcoming the NLO–LIDT incompatibility, being strikingly different from other reported approaches. This work provides new insights into optimizing the NLO performance of rare-earth IR NLO compounds through the modulation of octahedral motifs.

研究领域: 材料科学 · 光学 · 化学 · 物理学
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2022 · IF 4.326

One-Pot Method for the Synthesis of 2,5-Furandicarboxylic Acid from Fructose: In Situ Oxidation of 5-Hydroxymethylfurfural and 5-Acetoxymethylfurfural over Co/Mn/Br Catalysts in Acetic Acid

Heng Ban,Youwei Cheng,Lijun Wang,Xi Li

2,5-Furandicarboxylic acid (FDCA) derived from biomass is a versatile platform chemical for producing various degradable polymers, especially polyethylene 2,5-furandicarboxylate (PEF). To reduce the high cost of feedstock, fructose instead of expensive 5-hydroxymethylfurfural (HMF) was used as the feedstock for producing FDCA in the acetic acid (HOAc) solvent by a one-pot, two-step method. Fructose was first catalytically converted into HMF and 5-acetoxymethylfurfural (AMF) in HOAc over the Amberlyst-15 catalyst. After the separation of only Amberlyst-15, the in situ-formed HMF and AMF were further catalytically oxidized to FDCA by air (oxygen) over homogeneous Co/Mn/Br catalysts following the free-radical chain reaction mechanism. HOAc was not only used as the solvent for the dehydration and following oxidation process but also served as the effective co-catalyst for the dehydration of fructose. The effects of catalyst species, dosage, and reaction temperature on the dehydration process and oxidation temperature on FDCA yield and purity were evaluated systematically. Under the optimized reaction conditions, a total yield of HMF and AMF of 50% and a final FDCA yield of 35% were achieved. Combined with experimental results and theoretical calculation, the reaction mechanism for fructose dehydration side reactions and the HMF and AMF oxidation reactions was proposed correspondingly. The proposed two-step, one-pot method using fructose as the starting material is a promising route for the commercial production of FDCA with the simple operation and viable yield.

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ACS Applied Materials & Interfaces · 2023 · IF 9.5

Engineering CsPbX3 (X = Cl, Br, I) Quantum Dot-Embedded Borosilicate Glass through Self-Crystallization Facilitated by NaF as a Phosphor for Full-Color Illumination and Laser-Driven Projection Displays

Junhao Li,Dacheng Zhou,Ying Liu,Yan Chen,Jiayuan Chen,Yong Yang,Yuan Gao,Jianbei Qiu

All inorganic perovskite (CsPbX3, X = Cl, Br, I) quantum dot (QD) glass samples are considered the next generation of lighting materials for their excellent luminescence properties and stability, but crystallization conditions are difficult to control, which often leads to the inhomogeneous crystallinity of QDs. Here, we provided evidence that the presence of sodium fluoride induced self-crystallization of CsPbBr3 QDs during routine glass formation without the need for additional heat treatment. We showed that NaF simultaneously affected the network structure of glass and promoted the formation of CsPbBr3 QDs, that is, Na+ ions entered the glass network skeleton, partially interrupting the network structure, while the strong electronegativity of F– ions attracted Cs+ and Pb2+ ions into the gaps formed in the glass networks that had been loosened up by Na+ ions, which reduced the activation energy of crystallization processes. Our results showed that NaF-induced CsPbBr3 QDs glass had excellent thermal stability, high photoluminescence quantum efficiency (49%), and luminescent stability under high-power laser irradiation. Finally, this work also demonstrated the general applicability of this method in the making of a series of CsPbX3 (X = Cl, Br, I) QD glass samples by NaF-induced self-crystallization, which drastically expanded the color gamut to a range of full spectrum for luminescence and laser-driven projection displays. We believe that the work presented here represents a new direction for the research and development of full-color gamut inorganic perovskite quantum dot glass samples, which could have a significant impact on the future applications of laser-driven projection displays as well.

✓ 已验证 产品关联 DOI PubMed 高影响因子
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ACS Applied Nano Materials · 2024 · IF 5.3

Dual-Mode Luminescence from Polyacrylonitrile-Stabilized CsPbX3 (X = Br and I) Nanocrystals Triggered by NaYF4:Yb/Ln (Ln = Er and Tm) Upconversion Nanoparticles: Implications for Anticounterfeiting and Optical Thermometry

Mingye Ding,Xiaoyan Wang,Yinbiao Shi,Zixia Lin,Zhengtao Deng,Xiaofei Yang

Owing to their excellent photoelectric and optical properties, lead halide perovskite quantum dots (PeQDs) have attracted great attention and have broad applications in various fields. However, the shortcomings of poor stability and short-wavelength (ultraviolet/visible) excitation restrict their practical applications. Herein, to address the above issues, we report a polyacrylonitrile-based composite film containing CsPbX3 (X = Br and I) PeQDs and β-NaYF4:Yb/Ln (Ln = Tm and Er) upconversion nanoparticles (UCNPs) via an electrospinning strategy. Interestingly, all-inorganic CsPbX3 PeQDs are synthesized through an in situ growth process in polyacrylonitrile nanofibers, which provide a polymer matrix for the protection of PeQDs against decomposition under the effect of an external environment. Upon 980 nm laser irradiation, lanthanide-sensitized UC luminescence of stable CsPbX3 can be realized through radiative energy transfer from Tm3+/Er3+ ions to PeQDs. Consequently, dual-mode luminescence, including downshifting and UC with color-tunable outputs, can be observed from PeQDs under dual-wavelength excitation (UV and NIR). Benefiting from the special luminescent feathers (temperature-sensitive UC and dual-mode luminescence), the as-obtained composite nanofibers exhibit great potential in high-level anticounterfeiting and accurate noncontact thermometry.

✓ 已验证 产品关联 DOI 高影响因子
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JOURNAL OF MOLECULAR LIQUIDS · 2022 · IF 6.633

The effect of alkyl chain length of the imidazole ionic liquid surfactants on the improving lubricating properties of the hexagonal lyotropic liquid crystal composed of the [C16imCn]Br/hydrotalcite/H2O

Meiling Lei,Jing Sun,Yu Chen,Zixian Cai,Yimin Hu

The hydrotalcites were dispersed in the hexagonal lyotropic liquid crystals (LLCs) composed of 1-hexadecyl-3-alkyl imidazolium bromide ([C 16 imC n ]Br, n = 1, 2 and 3) and H 2 O. The effects of the hydrotalcite concentration and the alkyl chain length of the [C 16 imC n ]Br on the properties and the lubricant performance of the [C 16 imC n ]Br/hydrotalcite hexagonal LLCs were studied by small angle X-ray diffraction measurements, rheology and tribology. Compared with the pure hexagonal LLCs, the incorporation of hydrotalcite into the [C 16 imC n ]Br hexagonal LLCs can increase the interlayer distances and the viscoelasticity of the hybrid hexagonal LLCs gradually. However, the friction coefficient and wear volume decrease firstly and then increase with the increasing of hydrotalcite content. With the increase of the alkyl chain length of the [C 16 imC n ]Br, the viscoelasticity, the interlayer distance and the water permeability of the mixed LLCs gradually increase which decreases the friction coefficient and wear volume at the moderate hydrotalcite content. The mechanism of the effective improvement of lubrication performance of the hybrid hexagonal LLCs is the tribofilm formed by the physical adsorption and tribochemical reaction of [C 16 imC n ]Br/hydrotalcite LLCs on the steel surface.

CAS / MDL: 288-32-4
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2020 ·Vol. 22 ·期 30 ·17299-17305 · IF 3.43

Photoluminescence spectral broadening, chirality transfer and amplification of chiral perovskite materials (R-X-p-mBZA)2PbBr4 (X = H, F, Cl, Br) regulated by van der Waals and halogen atoms interactions

Chenyang Zhou,Ya Chu,Linlin Ma,Yingqian Zhong,Chao Wang,Yalan Liu,Haoyue Zhang,Beibei Wang,Xia Feng,Xi Yu,Xiaotao Zhang,Yan Sun,Xiaozeng Li,Guangjiu Zhao

In this work, we introduced halogen-substituted chiral molecules as A-site cations to synthesize a series of novel organic–inorganic hybrid two-dimensional (2D) chiral perovskite materials (R-X-p-mBZA)2PbBr4 (X = H, F, Cl, Br; p: para-position; mBZA = α-methylbenzylamine) for the first time. This halogen-substituted cation strategy collectively solved problems of narrow emission, weak chirality and low photoluminescence quantum yield (PLQY) for the emerged chiral perovskites. Photoluminescence (PL) spectra are significantly broadened due to the additional emission from self-trapped excitons (STEs) besides free excitons (FEs) states modulated by introducing significant disorder to the Pb–Br–Pb angle. The chirality of A-site chiral molecules is transferred and amplified to entire perovskite materials by fixing the chiral molecules at A-site via the interaction of halogen atoms. Furthermore, their PLQYs are improved with the reduction of energy gap and inhibition of the non-radiative transition from STEs to ground state. The halogen-substituted A-site cation strategy can be performed to develop organic–inorganic hybrid chiral perovskites with various optoelectronic applications.

CAS / MDL: 68-12-2 10031-22-8
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CHEMICAL ENGINEERING JOURNAL · 2024 · IF 13.3

Enhanced deep dehalogenation of brominated DBPs on vitamin B12 composite electrodes by the synergistic effect of UV irradiation: Accelerated formation of Co-Br bonds and enhanced mediation by atomic H*

Lei Wang,Hong Wang,Sinong Huang,Jiao Feng,Yifei Wu,Jing Deng,Junping Liu,Xiang Tu,Xiaoyan Ma,Xueyan Li,Andrea M. Dietrich

Complete dehalogenation of halogenated organic pollutants has attracted increasing attention, and electrocatalytic reduction processes are considered prospective technologies due to their high selectivity for carbon-halogen bonds. In this study, a vitamin B 12 (VB 12 ) composite electrode was prepared and applied to remove the refractory tribromoacetic acid (TBAA). The reduction process dominated by the VB 12 composite electrode showed a degradation efficiency of 55.2 % for 200 μg/L TBAA within 60 min. Interestingly, UV irradiation considerably increased the efficiency of TBAA for dehalogenation on the VB 12 composite electrode. The photoelectrochemical co-catalytic system of a VB 12 composite electrode coupled with UV (LP UV 254 nm) could remove 92.2 % of TBAA in 20 min with a rate constant 12 times higher than the VB 12 -only electrolysis system. The in situ Raman characterization and cyclic voltammetry tests confirmed that the accelerated formation of Co-Br bonds and the enhanced atomic H* mediated ability were responsible for improving debromination efficiency. The degradation of TBAA mainly underwent chemical reactions of debromination and mineralization. Acetic acid, formic acid, formaldehyde, and Br - were the major transformation products of TBAA. Acidic conditions favoured TBAA removal in the UV synergistic VB 12 electrolytic system, and excellent cycling stability of debromination was obtained in complex aqueous environments (actual bodies of water containing various inorganic and organic matter). This research provides an efficient dehalogenation technology for halogenated micropollutants and novel perspectives on the scientific design of photoelectrochemical dehalogenation processes.

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JOURNAL OF APPLIED POLYMER SCIENCE · 2025 · IF 2.8

Synthesis of Hyper-Crosslinked Polymers From 9-Bromophenanthrene and Octavinylsilsesquioxane for High Adsorption of Rhodamine B, Congo Red and I2 Vapor Assisting With C?Br⋯π Interaction

Rui Gao,Shen Zhang,Hailong Liu,Zhizhou Yang,Yue Wu,Sheng Gao,Mei Li,Hanlin Shao,Mingjie Wu

Disposal of dye-contaminated wastewater has become an imperative issue. Synthesis of novel materials for larger-capacity removal of those contaminants assisting by special interaction is a significant challenge. In this paper, a series of hyper-crosslinked poly 9-bromophenanthrene hybrids (HCPs) were synthesized by combination of 9-bromophenanthrene (9BP) and octavinylsilsesquioxane (OVS) via Friedel-Crafts alkylation reaction. The synthesized HCPs were well characterized. The results illustrated that HCPs were porous polymer hybrids consisting of micropores and mesopores with the apparent surface areas ( S BET ) in range of 980.0–1010.6 m 2 g −1 , and the micropore and mesopore widths located at 1.42 and 4 nm. Dye adsorption disclosed that the adsorbed amounts of rhodamine B (RB) and Congo red (CR) on HCP-2 respectively arrived at 2646.0 ± 37.4 and 1550.0 ± 38.5 mg g −1 , ascribing to the interactions of pore filling, hydrogen bonds, π  π stacking, electrostatic attraction, especially the C  Br⋯π interaction between the resulting polymers and the dye molecules of RB and CR. Moreover, HCP-2 exhibited larger adsorbed amount of iodine vapor arriving at 179.9 ± 2.6 wt%. This work provided an innovative strategy to design new adsorbents for larger-amount removal of contaminants from the environment.

CAS / MDL: 7446-70-0
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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2016 ·Vol. 18 ·期 27 ·18219-18226 · IF 4.449

The role of reduction extent of graphene oxide in the photocatalytic performance of Ag/AgX (X = Cl, Br)/rGO composites and the pseudo-second-order kinetics reaction nature of the Ag/AgBr system

Weiyin Gao,Chenxin Ran,Minqiang Wang,Le Li,Zhongwang Sun,Xi Yao

Although reduced graphene oxide (rGO)-based photocatalyst composites have been intensively developed during the past few years, the influence of reduction extent of rGO on the photocatalytic performance of the rGO-based composite has virtually not been investigated due to some technical limitations, such as the poor water dispersibility of rGO and low reduction selectivity of the hydrothermal method, which make it difficult to control the reduction extent of rGO in these composites. Herein, we used a facile room-temperature method to synthesize Ag/AgX (X = Cl, Br)/rGO photocatalyst composites as a model to study the effect of reduction extent of rGO on the photocatalytic performance of the photocatalyst. It was found that the photocatalytic activities of both Ag/AgCl/PrGO and Ag/AgBr/PrGO systems had an optimized threshold of the reduction extent of photoreduced GO (PrGO). More importantly, due to the different conductive band values of AgCl and AgBr, the optimized thresholds in the two systems were at different PrGO reduction extents, based on which we proposed that the favorable energy band matching between AgX and PrGO in the two systems played a crucial role in obtaining high photocatalysis performance. Besides, the photocatalytic reaction of the Ag/AgBr based system was confirmed to be a pseudo-second-order kinetics reaction rather than pseudo-first-order kinetics reaction. The new insights presented in this work provided useful information on the design and development of a more sophisticated photocatalyst, and can also be applied to many other applications.

研究领域: 材料科学 · 环境科学
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